Schlundt S, Kuzmanich G, De Miguel Rojas G, Kovács C, Garcia-Garibay MA, Guldi DM, Hirsch A (2009)
Publication Type: Journal article, Original article
Publication year: 2009
Original Authors: Schlundt S., Kuzmanich G., Spanig F., De Miguel Rojas G., Kovacs C., Garcia-Garibay M.A., Guldi D.M., Hirsch A.
Publisher: Wiley-VCH Verlag
Book Volume: 15
Pages Range: 12223-12233
Journal Issue: 45
A novel dendritic C-HP(ZnP) (P = porphyrin) conjugate gives rise to the successful mimicry of the primary events in photosynthesis, that is, light harvesting, unidirectional energy transfer, charge transfer, and charge-shift reactions. Owing, however, to the flexibility of the linkers that connect the Q, HP, and ZnP units, the outcome depends strongly on the rigidity/viscosity of the environment. In an agar matrix or Triton X-100, timeresolved transient absorption spectroscopic analysis and fluorescence-lifetime measurements confirm the following sequence. Initially, light harvesting is seen by the peripheral C-H P-*(ZnP) conjugate. Once photoexcited, a unidirectional energy transfer funnels the singlet excited-state energy to HP to form C-*(HP)-(ZnP), which powers an intramolecular charge transfer that oxidizes the photoexcited HP and reduces the adjacent C species. In the correspondingly formed (C)'(HP) -(ZnP) conjugate, an intramolecular charge-shift reaction generates (C)-HP-(ZnP) , in which the radical cation resides on one of the three ZnP moieties, and for which lifetimes of up to 460 ns are found. On the other hand, investigations in organic media (i.e., toluene, THF, and benzonitrile) reveal a short cut, that is, the peripheral ZnP unit reacts directly with C to form (C)H P-(ZnP) . Substantial configurational rearrangements-placing ZnP and C in proximity to each other-are, however, necessary to ensure the required through space interactions (i.e., close approach). Consequently, the lifetime of (C)'"-H P(ZnP) is as short as 100 ps in benzonitrile. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA,.
APA:
Schlundt, S., Kuzmanich, G., De Miguel Rojas, G., Kovács, C., Garcia-Garibay, M.A., Guldi, D.M., & Hirsch, A. (2009). Dendritic porphyrin-fullerene conjugates: Efficient light-harvesting and charge-transfer events. Chemistry - A European Journal, 15(45), 12223-12233. https://doi.org/10.1002/chem.200902161
MLA:
Schlundt, Sebastian, et al. "Dendritic porphyrin-fullerene conjugates: Efficient light-harvesting and charge-transfer events." Chemistry - A European Journal 15.45 (2009): 12223-12233.
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